Diazoamino dye intermediates



2,897,186 Patented July 28, 1959 2,897,186 DIAZOAlVllNO DYEINTERMEDIATES Julius Miller, Newark, NJ., and Dominic Del Guidice,Astoria, N.Y., assignors to Pharma-Chemical Corp., Bayonne, N.J., acorporation of New Jersey No Drawing. Application February 21, 1956Serial No. 580,159

19 Claims. (Cl. 260140) The present invention is directed to a textileprinting composition, more particularly to such compositions which yieldazo dyes in the printing operation. This ap .plication is acontinuation-in-part of copending application Serial No. 264,846, filedJanuary 3, 1952, now abandoned, and entitled Textile PrintingCompositions.

In recent years, there have been introduced compositions yielding azodyes for textile printing of cellulosic fibers, these dye compositionscontaining generally diazoamino compounds admixed with naphthoic acidarylid coupling components. While several such compositions are incommercial use, there is a difiicuflty in the use thereof in that it hasbeen necessary to age the composition with acid vapor in order todevelop the dye on the material being printed. Because of this there wasdifiiculty in handling the material; there were disadvantages in thecorrosiveness of the acid and in the disposal of the waste.

A number of attempts have been made to overcome these difiiculties anddisadvantages and it has been proposed to eliminate the acid aging bypreparing the final pigment in a water soluble form. This necessitatedthe use of other reagents and additional steps in the operation. Suchcomplications were serious and the compositions have been in verylimited use, if any. In another proposed method for eliminating the acidaging, certain specific diazotizable amines and certain amino carboxylicacids were used in the preparation of the diazoamino compound. However,the dyes thus formed are limited in the colors which may be obtained andproduce inferior shades, as a result of which they have not gone intogeneral use. Still other methods have been proposed but none of themhave been particularly successful.

The present invention is intended and adapted to overcome thedifiiculties and disadvantages inherent in prior methods of the typedescribed, it being among the objects of the present invention toprovide insoluble azo dyes from water soluble diazoamino compounds whichrequire no acid treatment or which may be formed by extremely shortexposure to acid.

It is also among the objects of the present invention to provide an.intermediate diazoamino compound which is utilized in the formation ofthe azo dye.

It is still further among the objects of the present invention toprovide a method of printing which embodies a high speed, developsbright colors and the dyes are fast to light and washing.

The invention is directed to a composition involving water-solublediazoamino compounds and coupling components, which require no acid andwhich may be set by steam only or which, by an extremely short exposureto acid, generates water-insoluble azo dyes.

The diazoamino compounds are formed by reacting secondary aromaticamines with aromatic diazotized amines. More specifically, thesediazoamino compounds are formed by condensing in alkaline aqueous mediuma diazonium solution of a diazotised aromatic amine devoid ofsolubilizing group such as sulfonic or carboxylic acids with asubstituted or unsubstituted alkyl or hydroxyl alkyl anthranilic acid ororthanilic acid. They have the following structural formula:

7L wherein R is the residue of a diazotized or tetrazotized aromaticmonoor diamine, A is an alkyl or hydroxyalkyl group having 1 to 5 carbonatoms, X is a carboxylic acid or sulfonic acid group, Y is hydrogen,halogen, nitro, alkyl, alkoxy and hydroxyalkyl in the meta or parapositions relative to the nitrogen, wherein the alkyl groups have from 1to 5 carbon atoms, and n is 1 when a monoamine is used and n is 2 when adiamine is used.

We have discovered that the above type diazoamino compounds regeneratethe diazonium originally used in its formation merely by subjecting itto elevated temperatures above room temperatures (about 20 C.) in thepresence of moisture. Thus in the presence of a coupling component azodye formation occurs. The dye yield is practically quantitative. No acidvapors are necessary, but they are not detrimental when used. In somecases a very short exposure to acid may be advantageous. When acidvapors are used, the exposure in the ager requires only lO30 seconds asagainst 3-5 minutes exposure commonly used in practice.

It was not to be expected that the aromatic secondary amine wouldcondense to form a diazoamino instead of condensing in the para positionto an azo dye. This reaction is quite unexpected and the reaction may berepresented by the following equation:

N HCHQOHiOH CHgCHaOH and? I I O OH This is directly contrary to what thechemists skilled in the art would expect to be the reaction, as normallythe following type of compound would be expected to result:

RN=N NHCHaOHgOH COOH This would be an azo dye.

Furthermore it Was not to be expected that such ease of hydrolysis tothe diazonium would occur. Moreover it was not to be expected that thediazoamino thus pr'e pared from a diazotised aromatic amine condensedwith a substance such as N-hydroxyethyl anthranilic acid to form thediazoamino of this structure- RN=N-l 'IOHzCHaOH COOH would, whenhydrolized by steam in presence of a cou pling component, couple to thedesired azo dye instead of the dye of the following structure:

l TCH2CHzOH 00011 I The latter coupling does not occur. The diazoniumformed couples smoothly with the coupling component chosen for a desiredazo pigment. The same holds true for the corresponding orthaniliccompound.

As diazotizable amines or tetrazotized diamines we utilize thosearomatic amines or diamines devoid of sulfonic or carboxylic groupsusually used to form the well known printing colors, such as thechlortoluidines, chloranisidines, nitrotoluidines, nitroanilines,nitroanisidines, cresidines, dianisidines, benzidines, tolidines, etc.By coupling components are meant the aceto-acetarylides andbeta-oxynaphthoic acid arylides and other coupling components such asamino naphthols and derivatives, pyrazolones, etc., devoid of groupslending solubility in water such as sulfonic or carboxylic groups.

The N-alkyl or N-hydroxy alkyl anthranilic or N-alkyl or N-hydroxy alkylorthanilic compounds are formed by condensing ortho-chlorbenzoic acid orits substituted derivatives or the ortho-chlorbenzol sulfonic acid orits substituted derivatives with the selected hydroxy-alkylamine oralkylamine, in the presence of copper as a catalyst at atmospheric orelevated pressure and at a temperature suitable for the condition of thereaction.

.These N-alkyl or N-hydroxyalkyl anthranilic or orthanilic compounds arereadily isolated as white crystalline compounds. The alkaline earthsalts are soluble in water and in excess mineral acid and consumenitrous acid readily to form a nitroso compound typical or aromaticsecondary amines. The aqueous solutions of the carboxylic acid metalsalts show a bluish fluorescence. The aqueous solution of the orthaniliccompound is not fluorescent.

By anthranilic acid we mean aminobenzene orthocarboxylic acid. Byorthanilic acid We mean aminobenzene orthosulfonic acid.

The following examples are illustrative of the present invention.

Example 1 12.85 parts by weight of the orange colored crystallinediazoamino compound, containing 0.02 pound moles efiective, formed bycondensing diaZotised-4-chlor-2- amino toluene at 2 C., with an alkalinesolution of a stoichiometric amount plus excess of Z-carboxy- N-hydroxyethyl amino benzene and isolated by means of addition of sodium chlorideand dried, are mixed with 0.02 pound moles of Z-hydroxynaphthoic acidortho toluidid. This mixture is dissolved by adding 1.5 lbs. sodiumhydroxide solution 26 B., 1.25 lbs. Cellosolve (ethylene glycolmonoethylether) and lbs. water. When completely dissolved, the solutionis thickened with sufficient ammonia neutralized starch-tragacanth pasteto total 50 lbs. This paste is now applied to cotton cloth by means of aprinting machine with copper rollers efiectiug a desired design as isthe usual practice well known in the art of textile printing. Theprinted cloth is then dried on the can and subsequently exposed to steamvapor at ZOO-212 F., in a vat ager without pressure. Any suitableapparatus or chamber may be used where the printed cloth is subjected tomoisture at an elevated temperature for at least three minutes. Theprinted material is then soaped in a mild soap bath, rinsed and dried.The cotton is now printed with the chosen design of a vivid full redshade, the probable formula of which is:

01 OH G 4-chlor-2-diazonitun chloride methoxy benzene and a 10% excessof N-hydroxyethyl anthranilic acid. The salted out diazoamino at firstprecipitates as an oil which on standing turns to a crystalline deposit.This is filtered, dried at low temperature.

6 lbs. of beta oxy naphthoic acid ortho anisidide (0.02 pound moles) areadded and allis dissolved by adding 1.5 lbs.. sodium hydroxide solution26 B., 1.25 lbs. Cellosolve and 15 lbs. water. When all in solution,starch-tragacanth paste which has been adjusted to a pH seven withammonia is added so that the total weight is 50 lbs. Printing anddevelopment is done as described above in Example 1. There results adesign in bright bluish rod. This red dye has the probable formula- OCH3(JO-NH .01

Commercial mixtures which yield this dye of the same probable formulaproduce no color when subjected to this development Without acid vapors.

Example 3 A printpaste prepared from 0.02 lb. moles in the form of a wetpress cake of the brownish-grey amorphorous diazoamino compound preparedfrom 4-chlor 2- diazonium chloride-toluene condensed in alkaline mediumat 2 C., with a 10% excess of 4-chlor-2-carboxy N- hydroxy ethylaniline, precipitated as a dense brown oil with sodium chloride andallowed to stand until it is amorphous and filterable.

5.6 lbs. of beta oxynaphthoic acid orthotoluidid.

1.5 lbs. sodium hydroxide solution 26 B.

1.5 lbs. Cellosolve and suflicient water to total 28 lbs.

This is stirred to solution and then thickened with 22 lbs. of starchtragacantli paste'or locust bean paste or sodium carboxy-methylcelluloseto a consistency suitable for textile printing and applied to cottoncloth; The printed cloth is developed as described above. The dye is thesame color as in Example 1.

g Example 4 A print paste is prepared from 0.02 lb. moles of thediazoamino obtained by condensing 4-nitro 2 diazonium chloride-anisoleand a 10% excess of 4- chlor 2-sulfo N- 'methyl aniline at 0 C., andisolating by means of salting with sodium chloride, filtering and dryingin vaccue at 45 C.

6.25 lbs. naphthol A S B S (Beta-hydroxy naphthoic acidmeta-nitroanilide), 1.5 lbs.. sodium hydroxide solution 26 B and 2.0lbs. Cellosolve (ethyl ether of diethylene glycol) are mixed withsufiicient water to make 30 lbs. ,Total solution is achieved. bystirring and then the solution is thickened with 20 lbs. of asuitablecolloid for applying the paste to cotton cloth.

After can drying, the printed cloth is passed through a Mather-Platteager in which a mixture of formicacetic acid vapors are mixed with livesteam. The cloth passes through these vapors in twenty seconds. Aftersoaping and rinsing and pressing there results a vivid bluish red, theprobable formula of which is- '01. we." No,

Commercial compositions containing Naphthol A S B S admixed withstabilized'diazonium of para-nitro'orthoanisidines when subjected to thesame treatment show but a stain as compared with the full developmentsof our mixture. 'This is due to the short time exposure which results ina very low yield of azo dye formation.

The above specific examples are intended to illustrate the wide varietyof reactants which may be used in accordance with the invention. Manyother coupling components, nitrogen bases and diazonium compounds whichare suitable for the present purposes are described in the literature.The book by K. Venlcataraman entitled The Chemistry of Synthetic Dyes,published in 1952 by Academy Press, Inc., vol. 1, describes many suchcompounds, and on page 660, Table 2, gives a list of amines which is byno means complete. Also, the book by Louis Diserens entitled TheChemical Technology of Dyeing and Printing, published in 1948 byReinhold Publishing Corp. gives such a list of amines on page 364, Table6. The disclosures of both of these books are made a part hereof byreference.

We claim:

1. A dye intermediate having the following structural formula:

wherein R is a residue taken from the class consisting of diazotized andtetrazotized aromatic mono and diamines, said amines being free fromsulfonic and carboxylic acid groups, A is a radical taken from the classconsisting of alkyl and hydroxy-alkyl having 1 to 5 carbon atoms, X is asingle radical taken from the class consisting of carboxylic acid andsulfonic acid, Y is a radical in a position taken from the classconsisting of meta and para to the nitrogen and taken from the classconsisting of hydrogen, halogen, nitro, alkyl, alkoxy and hydroxyalkyl,the alkyl groups having from 1 to 5 carbon atoms, and n is 1 when amonoamine is used and n is 2 when a diamine is used.

2. A dye intermediate according to claim 1 in which the aromatic amineis chlortoluidine.

3. A dye intermediate according to claim 1 in which the aromatic amineis chloranisidine.

4. A dye intermediate according to claim 1 in which the aromatic amineis nitrotoluidine.

5. A dye intermediate according to claim 1 in which the aromatic amineis nitroaniline.

6. A dye intermediate according to claim 1 in which the aromatic amineis nitroanisidine.

7. A dye intermediate according to claim 1 in which the aromatic amineis cresidine.

8. A dye intermediate according to claim 1 in which the aromatic amineis dianisidine.

9. A dye intermediate according to claim 1 in which the aromatic amineis benzidine.

10. A dye intermediate according to claim 1 in which the aromatic amineis tolidine.

11. A dye intermediate having the following structural formula:

COOH

wherein R is a residue taken from the class consisting of diazotized andtetrazotized substituted aromatic monoand di-amines in which said aminesare free from sulfonic and carboxylic acid groups, n is 1 when amonoamine iSuSBdandnisZWhen a diamineisused.

12. A dye intermediate having the following structural formula:

13. A dye intermediate having the following structural formula:

COOH

14. A dye intermediate having the following structural formula:

15. A dye intermediate having the following structural formula:

16. A dye intermediate having the following structural...

formula:

GOOH

CODE

References Cited in the file of this patent UNITED STATES PATENTS2,078,387 Kern Apr. 27, 1937 2,124,594 Schmelzer July 26, 1938 2,422,359Maynard June 17, 1947 2,675,374 Petitcolas et al. Apr. 13, 1954

1. A DYE INTERMEDIATE HAVING THE FOLLOWING STRUCTURAL FORMULA: